Schiff 碱双核配合物的磁性及催化性能的研究

This paper reports the catalytic properties of “porphyrin-like” Schiff base mononuclear complexes MH₂L {M=Mn(Ⅱ), Fe(Ⅲ)Cl, Cr(Ⅲ)Cl, Cu(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Zn(Ⅱ); L=bis[N, N′-ethylene-2, 2′-(phenylmethylene)bis(3,4-dimethylpyrrole-5-aldimino)]} and dinuclear complexes MnML [M=Mn(Ⅱ), Fe(Ⅲ)Cl, Cr(Ⅲ)Cl, Cu(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Zn(Ⅱ)] for cyclohexane monooxygenation with PhIO and magnetic properties of the dinuclear complexes. The magnetic investigations (4～300 K) of the dinuclear complexes revealed that their antiferromagnetic spin exchange with J ranged from -10.49 to -0.482 cm^-1 except MnZnL and antiferromagnetic spin exchange decreased in the following order: Mn^Ⅱ-Cu^Ⅱ > Mn^Ⅱ-Ni^Ⅱ > Mn^Ⅱ-Mn^Ⅱ > Mn^Ⅱ-Fe^Ⅲ > Mn^Ⅱ-Co^Ⅱ > Mn^Ⅱ-Cr^Ⅲ. The results of catalyzed oxidation of cyclohexane indicated that the catalytic property of the dinuclear complex was better than that of the corresponding mononuclear complex. It was found that there was the synergism decreased in the order: Mn-Fe > Mn-Cr > Mn-Cu > Mn-Mn > Mn-Co> Mn-Ni > Mn-Zn. It seems that this synergism increases with the increase of the number of unpaired d electrons and the magnetic exchange between the two metals in these dinuclear complexes.     

新型呋喃基取代卟啉的合成及荧光性能

利用呋喃甲醛与二(3,4-二甲基吡咯)-芳基甲烷在醋酸中加热回流的方法,合成了6种新型2,3,7,8,12,13,17,18-八甲基-5,15-二芳基-10,20-二呋喃基卟啉化合物,其结构均经UV-Vis、IR、1HNMR确证.这些化合物均能发射较强的红光.     

卟啉化合物荧光性能的取代基效应研究

研究了12种四芳基卟啉化合物荧光性能的取代基效应.结果表明,卟啉化合物的苯基上供电子取代基能增加卟啉的荧光强度,而吸电子取代基作用相反;荧光强度随着卟啉的苯环上取代基卤素原子量的增加而降低;此外,荧光强度还与卟啉的苯环上取代基的取代位置有关.